Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

• This invention relates to a photopolymerisation and photocrosslinking process, and in particular to such a process for the production of images.
• this object can be achieved by the use of certain substances which contain in the molecule two kinds of groups through which photopolymerisation can occur at rates which differ considerably from one another.
• the groups are chosen so that photopolymerisation of a layer of a liquid composition occurs rapidly to form a solid, essentially tack-free layer, which is, however, still soluble in certain solvents.
• parts of the layer are further subjected to a substantially greater amount of actinic radiation and photocrosslinking takes place through the other type of group in the already photopolymerised molecules of the layer, the parts of the layer which undergo photocrosslinking becoming much more resistant to solution in the solvents.
• the desired process can be achieved by employing a compound which contains in the same molecule both one or more acryloyl or methacryloyl groups and one or more 2,3-disubstituted maleimide groups.
• One aspect of this invention accordingly provides a process for production of an image which comprises
• R denotes a hydrogen atom or a methyl group
• R 1 and R 2 each denote the same or different alkyl group of 1 to 4 carbon atoms or together they denote a trimethylene or tetramethylene group which may be optionally substituted by a methyl group.
• British Patent Specification No. 1 544 840 describes the preparation of numerous compounds containing 2,3-disubstituted maleimide units, particularly 2,3-dimethylmaleimido units, including some which also contain acryloyl or methacryloyl groups.
• British Patent Specification No. 1 544 299 describes polymers containing 2,3-disubstituted maleimide units which can be crosslinked by means of actinic radiation.
• monomers which contain, in addition to the double bond present in the 2,3-disubstituted maleimido radical of formula II, a further ethylenically unsaturated double bond which can be polymerised more easily than the 2,3-disubstituted maleimido radical of formula II can be polymerised by means of free radical initiators in such a way that polymers are obtained which do not have a crosslinked structure, which contain the 2,3-disubstituted maleimido groups of formula II as side substituents, and which can subsequently be crosslinked by means of electromagnetic irradiation.
• N-(3-(acryloyloxy)propyl)-2,3-dimethylmaleimide together with methyl methacrylate, glycidyl methacrylate, ethyl acrylate, or 2-hydroxyethyl acrylate, was polymerised by means of benzoyl peroxide or 2,2'-azobis(2-methylpropionitrile). That the vinyl polymerisations were all effected using chemical free radical initiators suggests that the vinyl polymerisations to obtain polymers containing 2,3-disubstituted maleimido groups which are still photopolymerisable could not be carried out using actinic radiation.
• the compound (A) employed in the process of this invention will contain, per average molecule, up to four groups of formula I and up to four groups of formula II. Preferably it has a molecular weight of at most 2,000.
• the group or groups of formula I, and preferably also the group or groups of formula II are each directly attached to an atom or atoms or carbon, oxygen, or nitrogen; particularly preferred are compounds in which R 1 and R 2 in formula II each denote a methyl group.
• Compounds suitable for use as (A) may be obtained by reaction, simultaneously or in either order, of a compound having two or more glycidyl groups directly attached to an atom or atoms of oxygen, nitrogen, or sulphur with acrylic or methacrylic acid and with a 2,3-disubstituted maleimido-carboxylic acid of formula ##STR3## where
• R 1 and R 2 have the meanings assigned in formula II and
• R 3 denotes a divalent residue, after removal of a primary amino group and a carboxyl group, of a compound containing at least one said amino group and at least one carboxyl group, preferably an aliphatic, cycloaliphatic, aromatic, araliphatic, or heterocyclic residue of 1 to 12 carbon atoms.
• a and b are each independently an integer of at least 1 and preferably at most 4,
• R 1 and R 2 have the meanings assigned in formula II,
• R 3 has the meaning assigned in formula III, and
• R 4 denotes the residue, after removal of (a+b) glycidyl groups directly attached to an atom or atoms of oxygen, nitrogen, or sulphur, of a compound containing at least (a+b) such glycidyl groups.
• the product will also contain adducts formed from the compound having two or more glycidyl groups and from acrylic acid or methacrylic acid only, or from the compound containing two or more glycidyl groups and from the 2,3-disubstituted maleimido-carboxylic acid only, i.e., compounds of formula ##STR5## and compounds of formula ##STR6## where
• c represents zero or a positive integer
• d is an integer of at least one, the sum of (c+d) being the same as the sum of (a+b),
• R 1 and R 2 have the meanings assigned in formula II,
• R 3 has the meaning assigned in formula III, and
• R 4 has the meaning assigned in formula IV.
• Carboxylic acids of formula III are obtainable by reaction of a 2,3-disubstituted maleic anhydride with an aminoacid of formula H 2 NR 3 COOH as described in the aforementioned British Patent Specification No. 1 544 840.
• R 3 may represent, by way of example, a p-phenylene, methylene, ethylene, pentamethylene, or ethylidene group.
• R 1 and R 2 has the meanings assigned in formula II and
• R 5 denotes the divalent residue, after removal of a primary amino group and a phenolic hydroxyl group, of a compound containing at least one said amino group and at least one said hydroxyl group, preferably an aromatic residue of 6 to 18 carbon atoms,
• R 1 and R 2 have the meanings assigned in formula II,
• R 4 has the meaning assigned in formula IV
• R 5 has the meaning assigned in formula VII, and
• Phenols of formula VII are obtainable by reaction of a 2,3-disubstituted maleic anhydride with an aminophenol of formula H 2 NR 5 OH as described in the aforementioned British Patent Specification No. 1 544 840.
• R 5 may represent, by way of example, an o--, m--, or p-phenylene group.
• the product will also contain adducts formed from the compound having two or more glycidyl groups and from acrylic or methacrylic acid only, or from the compound having two or more glycidyl groups and from the 2,3-disubstituted maleimido-phenol only, i.e., compounds of formula V and compounds of formula ##STR9## where
• R 1 and R 2 have the meanings assigned in formula II,
• R 3 has the meaning assigned in formula III
• R 4 has the meaning assigned in formula IV
• R 5 has the meaning assigned in formula VII, and
• polyglycidyl esters obtainable by reaction of a compound containing two or more carboxylic acid groups per molecule with epichlorohydrin or with glycerol dichlorohydrin in the presence of an alkali.
• Such polyglycidyl esters may be derived from aliphatic polycarboxylic acids, e.g., succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, or dimerised or trimerised linoleic acid; from cycloaliphatic polycarboxylic acids such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid, and 4-methylhexahydrophthalic acid, and from aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid.
• Other suitable polyglycidyl esters are obtainable by polymerisation of glycidyl esters of vinylic acids, especially glycidyl acrylate and glycidyl methacrylate.
• polyglycidyl ethers obtainable by reaction of a compound containing at least two free alcoholic hydroxyl and/or phenolic hydroxyl groups per molecule with epichlorohydrin under alkaline conditions or, alternatively, in the presence of an acidic catalyst and subsequent treatment with alkali.
• ethers may be made from acryclic alcohols such as ethylene glycol, diethylene glycol, and higher poly(oxyethylene) glycols, propane-1,2-diol and poly(oxypropylene) glycols, propane-1,3-diol, poly(oxytetramethylene) glycols, pentane-1,5-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol, sorbitol, and polyepichlorohydrins; from cycloaliphatic alcohols such as resorcitol, quinitol, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane, and 1,1-bis(hydroxymethyl)cyclohex-3-ene; and from alcohols having aromatic nuclei, such as N,N-bis(2-hydroxyethyl
• they may be made from mononuclear phenols, such as resorcinol and hydroquinone, and from polynuclear phenols, such as bis(4-hydroxyphenyl)methane (otherwise known as bisphenol F), 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl) sulphone, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (otherwise known as bisphenol A), 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, and novolaks formed from aldehydes such as formaldehyde, acetaldehyde, chloral, and furfuraldehyde, with phenol itself, and phenol substituted in the ring by chlorine atoms or by alkyl groups each containing up to nine carbon atoms, such as 4-chlorophenol, 2-methylphenol, and 4-tert.-butylphenol.
• Poly(N-glycidyl) compounds may also be used, e.g., N-glycidyl derivatives of amines such as aniline, n-butylamine, bis(4-aminophenyl)methane, and bis(4-methylaminophenyl)methane; triglycidyl isocyanurate; and N,N'-diglycidyl derivatives of cyclic alkylene ureas, such as ethyleneurea and 1,3-propyleneurea, and of hydantoins such as 5,5-dimethylhydantoin.
• amines such as aniline, n-butylamine, bis(4-aminophenyl)methane, and bis(4-methylaminophenyl)methane
• triglycidyl isocyanurate and N,N'-diglycidyl derivatives of cyclic alkylene ureas, such as ethyleneurea and 1,3
• Poly(S-glycidyl) compounds may also be used, e.g., di(S-glycidyl) derivatives of dithiols such as ethane-1,2-dithiol and bis(4-mercaptomethylphenyl) ether, but they are not preferred.
• Polyepoxides having the 1,2-epoxide groups attached to different kinds of hetero atoms may be employed, e.g., the glycidyl ether-glycidyl ester of salicylic acid, or p-(diglycidylamino)phenyl glycidyl ether.
• R 4 represents the divalent residue of a polyglycidyl ether, which may have been advanced, of a polyhydric phenol or of a polyhydric aliphatic alcohol.
• Compounds suitable for use as component (A) may also be obtained by reaction of a compound containing two or more alcoholic hydroxyl groups with acryloyl or methacryloyl chloride and with a 2,3-disubstituted maleimido-acid chloride of formula ##STR10## where
• R 1 and R 2 have the meanings assigned in formula II and
• R 3 has the meaning assigned in formula III.
• R 1 and R 2 have the meanings assigned in formula II,
• R 3 has the meaning assigned in formula III, and
• R 6 denotes the residue, after removal of (a+b) alcoholic hydroxyl groups, of an alcohol having at least (a+b) said hydroxyl groups.
• R 6 denotes an aliphatic residue comprising repeating units of formula
• R 6 may, for example, represent the residue of a poly(oxyethylene) glycol or poly(oxypropylene) glycol of average molecular weight 250 to 5000, or the residue of a polyvinyl alcohol of average molecular weight 500 to 9000.
• R 1 and R 2 have the meanings assigned in formula II,
• R 3 has the meaning assigned in formula III, and
• R 6 has the meaning assigned in formula XI.
• component (A) is of the general formula ##STR15## or of the general formula ##STR16## where
• R 1 and R 2 have the meanings assigned in formula II,
• R 3 has the meaning assigned in formula III, and
• R 5 has the meaning assigned in formula VII.
• Compounds of formula XV and XVI may be obtained by reaction of glycidyl acrylate or glycidyl methacrylate with, respectively, a 2,3-disubstituted maleimido-carboxylic acid of formula III and a 2,3-disubstituted maleimido-phenol of formula VII.
• R 1 and R 2 have the meanings assigned in formula II,
• R 7 denotes an alkylene group of 2 or 3 carbon atoms
• R 8 denotes a hydrogen atom or a group of formula ##STR18##
• Such compounds where R 8 denotes a hydrogen atom may be obtained by reaction of a sodium salt of an aminophthalic acid with a disubstituted maleic anhydride in toluene-water followed by acidification to isolate the 2,3-disubstituted maleimidophthalic acid and dehydration to form the anhydride and then reaction with a hydroxyalkyl acrylate or methacrylate as described in the above-mentioned British Patent Specification No. 1,544,299.
• 3-(2,3-dimethylmaleimido)phthalic anhydride may be converted, by means of 2-hydroxyethyl methacrylate, into 2-(5-methyl-3-oxa-4-oxohex-5-enyloxycarbonyl)-6-(2,3-dimethylmaleimido)benzoic acid.
• R has the meaning assigned in formula I and
• R 1 and R 2 have the meanings assigned in formula II.
• Reaction of a phenylenediamine with a disubstituted maleic anhydride can be conducted such as to furnish the mono-substituted imide-amine as disclosed in the above-mentioned British Patent Specification No. 1,544,840, which imide-amine may then be treated with (meth)acryloyl chloride in a conventional manner to form an imide-amide of formula XX.
• R has the meaning assigned in formula I and
• R 1 and R 2 have the meanings assigned in formula II,
• R 1 and R 2 have the meanings assigned in formula II, and
• R 9 denotes a divalent residue, after removal of a primary amino group and an alcoholic hydroxyl group, of a compound containing at least one said amino group and at least one said hydroxyl group, preferably an aliphatic residue of 2 to 6 carbon atoms or a cycloaliphatic residue of 6 to 8 carbon atoms, which may also be employed, may be made by reaction of a disubstituted maleimido-alcohol of formula ##STR22## with N-(hydroxymethyl)acrylamide, N-(hydroxymethyl)methacrylamide, or the corresponding N-(methoxymethyl) compounds.
• R 1 and R 2 have the meanings assigned in formula II, and
• R 5 has the meaning assigned in formula VII,
• (A) is of the general formula ##STR24##
• R 1 and R 2 have the meanings assigned in formula II, and
• R 10 denotes an imino group, an alkylenoxy group of 1 to 10 carbon atoms, a 2-hydroxypropyleneoxy group, a poly(oxyalkylene) group of 4 to 12 carbon atoms, a cycloalkyleneoxy group of 5 to 7 carbon atoms, or an alkylenecarbonamide group of 2 to 10 carbon atoms.
• R 10 may represent, for example, an alkylenecarbonamido group of formula --(CH 2 ) 5 CONH--, an alkyleneoxy group of formula --(CH 2 ) 6 O--, a cyclohexyleneoxy group, or a methylcyclohexyleneoxy group; preferably it denotes a group of formula --(CH 2 ) m-1 O--, --CH 2 CH(CH 3 )O---, --CH 2 CH(OH)CH 2 O--, ##STR25## where m has the meaning assigned in formula XII.
• Such compounds where R 10 represents --CH 2 CH(OH)CH 2 O-- may be obtained by reaction of an N-glycidyl-2,3-disubstituted maleimide with acrylic acid or methacrylic acid.
• Compounds of formula XXV where R 10 denotes a cycloalkeneoxy group may be obtained by reaction of a 2,3-disubstituted maleic anhydride with a cycloaliphatic aminoalcohol followed by treatment with acryloyl chloride or methacryloyl chloride.
• substances suitable for use as compound (A) are N-(2-(acryloyloxy)ethyl)-2,3-dimethylmaleimide, N-(3-acryloyloxy)-2-hydroxypropyl)-2,3-dimethylmaleimide, N-(3-(acryloyloxy)propyl)-2,3-dimethylmaleimide, the corresponding methacryloyl homologues, N-(2-(2-methacryloyloxy)ethoxy)ethyl)-2,3-dimethylmaleimide, and the 2-(acryloyloxy)ethyl 3-(methacryloyloxy)-2-hydroxypropyl esters of 3- and 4-(2,3-dimethylmaleimido)phthalic acids.
• the liquid composition contain an added photoinitiator, i.e., a catalyst which, on irradiation, gives an excited state that leads to formation of free radicals which then initiate polymerisation of (A).
• photoinitiators are organic peroxides and hydroperoxides, ⁇ -halogen substituted acetophenones such as trichloromethyl 4'-tert.
• butylphenyl ketone ⁇ -hydroxy- ⁇ -alkyl-substituted acetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin and its alkyl ethers (e.g., the n-butyl ether), ⁇ -methylbenzoin, alkyl ⁇ , ⁇ -dialkyloxy- ⁇ -benzoylacetates, benzophenones such as benzophenone itself and 4,4'-bis(dimethylamino)benzophenone, O-alkoxycarbonyl derivatives of an oxime of benzil or of 1-phenylpropane-1,2-dione, such as benzil (O-ethoxycarbonyl)- ⁇ -monoxime and 1-phenylpropane-1,2-dione 2-(O-ethoxycarbonyl)oxime, benzil ketals, e.g., its dimethyl ketal, substituted thioxanthones, e
• Suitable photoinitiators are readily found by routine experimentation. Generally, 0.15 to 10%, and preferably 2.5 to 5%, by weight of the photoinitiator is incorporated, based on the total weight of (A) and any further compound (B) present containing at least one group of formula I but none of formula II. (Substances suitable for use as compound (B) are described below.)
• the liquid composition further contain an added triplet photosensitiser, i.e., a compound which, on irradiation, gives an excited state that transfers the triplet energy to a 2,3-disubstituted maleimide group of formula II which is not excited.
• triplet sensitiser display an absorption maximum which permits a light absorption in the range of more than 300 nm which is adequate for practical purposes, and it is also required that the triplet energy transfer be exothermic.
• Photopolymerised compounds containing the 2,3-disubstituted maleimide group of formula II have a T 1 state which lies between 50 and 53 kCal.
• triplet sensitisers which permit exothermic energy transfer in the range mentioned, that is to say, have a T 1 state of at least 50 kCal. per mol. are suitable for sensitising.
• suitable sensitisers are benzene, phenol, benzoic acid, benzonitrile, aniline, xanthone, acetophenone, di-isopropyl ketone, diphenyl sulphide, diphenylamine, benzaldehyde, diphenylselenium, carbazole, triphenylamine, hexachlorobenzene, 4,4-diphenylcyclohexadienone, 1,2-dibenzoylbenzene, thiophene, benzophenone, 1,4-diacetylbenzene, fluorene, triphenylene, 4 -cyanobenzophenone, diphenyl, thioxanthone, 2-chlorothioxanthone,
• Suitable photosensitisers are likewise readily found by routine experimentation. Generally, 0.1 to 10%, and preferably 0.5 to 7.5%, by weight of the photosensitiser is incorporated, calculated on the total weight of (A) and any other compound (C) present containing at least one group of formula II but none of formula I.
• the composition is applied in a liquid form to a carrier.
• its viscosity is in the range 0.1 to 0.4 Pa s.
• the composition may be liquid it may be necessary, in order to achieve this without the use of volatile organic solvents, to include another compound which is a liquid and which photopolymerises under the conditions in stage (1) to form a solid.
• a photopolymerisable compound (B) having in the molecule at least one group of formula I but none of formula II.
• Compound (B) may be, for example, an alkyl or hydroxyalkyl ester (which alkyl or hydroxyalkyl group may be substituted) of acrylic acid or methacrylic acid, typically, such esters having up to 15 carbon atoms in all, such as methyl methacrylates, ethyl methacrylate, n-butyl acrylate, and 2-hydroxyethyl acrylate. Also useful for this purpose are 3-alkoxy-2-hydroxypropyl, 3-alkenoxy-2-hydroxypropyl, and 3-aryloxy-2-hydroxypropyl esters of acrylic acid or methacrylic acid, typically, those containing up to 15 carbon atoms in all.
• compound (B) may be included in the liquid composition so that some desired property may be imparted to the photopolymerised, photocrosslinked product.
• the compound (B) may also contain at least one chlorine, bromine, or phosphorus atom.
• aryl glycidyl ether such as dibromo-p-cresyl glycidyl ether, e.g., 3-(methacryloyloxy)-2-hydroxypropyl X,Y-dibromo-p-cresyl ether.
• epoxide groups may be desirable to introduce epoxide groups into the composition: after the product has been photocrosslinked, additional crosslinking may be achieved by thermal curing through epoxide groups. It may therefore be advantageous to include in the liquid composition a photopolymerisable compound having in the same molecule both a group of formula I and only one 1,2-epoxide group, such as glycidyl acrylate or glycidyl methacrylate. Alternatively, an epoxide resin (i.e., a compound containing more than one epoxide group) may be included in the liquid composition before photopolymerisation.
• the liquid composition may likewise contain a photopolymerisable compound (C) having at least one group of formula II but none of I, e.g., N-glycidyl-2,3-dimethylmaleimide.
• the liquid composition can be applied to suitable carriers by the customary techniques, such as spray coatings, whirler coating, roller coating, cascade coating, and especially curtain coating.
• the carrier is coated such that the layer of the composition is 1 to 250 ⁇ m thick.
• the carrier may be of, for example, copper, aluminium or other metal, paper, synthetic resin, or glass.
• actinic radiation of wavelength 200-600 nm is preferably used.
• Suitable sources of actinic radiation include carbon arcs, mercury vapour arcs, fluorescent lamps with phosphors emitting ultraviolet light, argon and xenon glow lamps, tungsten lamps, and photographic flood lamps. Of these, mercury vapour arcs, particularly sun lamps, fluorescent sun lamps, and metal halide lamps are most suitable.
• the times required for the exposures of the photopolymerisable composition and the still photocrosslinkable composition will depend upon a variety of factors which include, for example, the individual compounds used, the type of light source, and the distance of that source from the irradiated composition.
• Suitable times may be readily determined by those familiar with photopolymerisation techniques; usually, the amount of light energy required in the second stage (the photocrosslinking stage) is 15 to 100 times that required in the first stage, typically, 25 to 60 times.
• the composition is first irradiated at a distance of 10-25 cm with a 500 watt bulb for 5-15 seconds: in the second stage it is irradiated for 10-20 minutes at a distance of 15-30 cm.
• the irradiation times, particularly in the second stage may be much shorter.
• the preferred substances for use as compound (A) contain only one group of formula I per molecule, but satisfactory results have been achieved with substances containing more than one such group.
• diacrylates, dimethacrylates and other substances containing more than one group of formula I are used, exposure to actinic radiation in stage (1) should be restricted so that any crosslinking in that stage through groups of formula I does not proceed to an extent such that formation of an image in stage (3) is substantially inhibited.
• Suitable solvents for development of the image are readily found by routine testing and include cyclohexanone, trimethylcyclohexanone, 2-ethoxyethanol, 1,1,1-trichloroethane, benzyl alcohol, methylene chloride, and mixtures thereof.
• the action of the solvent may need to be assisted by agitation or by gentle brushing.
• the carrier has a layer of a suitable electrically-conducting metal, usually copper or silver, immediately in contact with the photopolymerised composition uncrosslinked polymer can be removed by development to expose the metal. Metal so exposed may then be etched away in the non-image areas, so forming a printed circuit, by means of etching fluids such as ferric chloride or ammonium persulphate solutions.
• a compound (B) which also has at least one free sulphonic or phosphonic acid group, or particularly at least one free carboxylic acid group; conveniently, this is acrylic acid or methacrylic acid or an adduct of a hydroxyalkyl acrylate or methacrylate with trimellitic anhydride, i.e., a compound of formula ##STR26## where either R 11 denotes a hydrogen atom, in which case R 12 denotes a group of formula ##STR27## or
• R 11 denotes a group of formula XXVIII or XXIX, in which case R 12 denotes a hydrogen atom, wherein
• R has the meanings assigned in formula I and
• the presence of free sulphonic, phosphoric, or carboxylic acid groups in the photopolymerised polymer has as a consequence the facility of using an aqueous solution of a base, such as dilute sodium hydroxide, sodium carbonate, disodium hydrogen orthophosphate, or ammonia solutions for development, thus avoiding the use of organic solvents in this stage.
• a base such as dilute sodium hydroxide, sodium carbonate, disodium hydrogen orthophosphate, or ammonia solutions for development
• a compound (B) which also has at least one primary, secondary, or tertiary amino group.
• aqueous solutions of acids may be used as the developer, such as dilute solutions of mineral acids.
• examples of such compounds (B) are alkyl esters of acrylic or methacrylic acid, which alkyl groups are substituted by a secondary or tertiary amino group, such as 2-(dimethylamino)ethyl methacrylate.
• the composition after photopolymerisation and photocrosslinking may contain an epoxide resin in which case it may also contain a latent, heat-curing agent for the epoxide resin so that the composition may be heated and supplementary crosslinking occur, further to increase the resistance of the photocrosslinked product to solvents and high temperatures.
• the epoxide resin may, as already stated, be included as such in the composition or may be formed in situ through photopolymerisation of a compound (B) which also contains in the same molecule only one 1,2-epoxide group.
• latent, heat-curing agents for epoxide resins are polycarboxylic acid anhydrides, such as hexahydrophthalic anhydride, dicyandiamide, complexes of amines such as ethylamine, trimethylamine, and n-octyldimethylamine with boron trifluoride or with boron trichloride, latent boron difluoride chelates, aromatic polyamines such as bis(p-aminophenyl)methane and bis(p-aminophenyl) sulphone, aromatic biguanides such as 2,6-xylidene biguanide, and imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole.
• polycarboxylic acid anhydrides such as hexahydrophthalic anhydride, dicyandiamide, complexes of amines such as ethylamine, trimethylamine, and n
• This mixture was prepared similarly, from mixed o-, m-, and p-cresyl glycidyl ethers.
• a composition comprising 45 parts of N-(2-(methacryloyloxy)ethyl)-2,3-dimethylmaleimide, 45 parts of mixed 3-(methacryloyloxy)-2-hydroxypropyl cresyl ethers, 8 parts of benzil dimethyl ketal, and 2 parts of 2-chlorothioxanthone was prepared by heating the methacrylates together at about 50° C. and then stirring in the photoinitiator and the photosensitiser to dissolve them.
• This composition which had a viscosity of about 0.25 Pa s, was applied by a spin coater as a layer approximately 20 ⁇ m thick onto copper plate. The coating was irradiated for 15 seconds with a medium pressure mercury lamp (80 w per cm) at a distance of 20 cm, and the coating became nontacky.
• the coating was irradiated through a negative at a distance of 25 cm from a medium pressure mercury lamp (30 w per cm) for 10 minutes, followed by development with cyclohexanone. A good relief image was obtained.
• Example 2 The procedure of Example 1 was repeated, using a composition which had a viscosity of about 0.3 Pa s and comprised 25 parts of N-(2-(methacryloyloxy)ethyl)-2,3-dimethylmaleimide, 56 parts of 3-(methacryloyloxy)-2-hydroxypropyl X,Y-dibromo-p-cresyl ether, 11 parts of glycidyl methacrylate, 7 parts of benzil dimethyl ketal, and 2 parts of 2-chlorothioxanthone.
• the coating was irradiated for 10 seconds in the first stage and for 15 minutes in the second stage.
• the image was developed in a mixture of equal parts by volume of 1,1,1-trichloroethane and cyclohexanone with agitation and brushing. A good relief image was obtained.
• Example 1 The procedure of Example 1 was repeated, using a composition which comprised 41.7 parts of N-(2-(methacryloyloxy)ethyl)-2,3-dimethylmaleimide, 41.7 parts of 3-(methacryloyloxy)-2-hydroxypropyl X,Y-dibromo-p-cresyl ether, 10 parts of glycidyl methacrylate, 5 parts of benzil dimethyl ketal, and 1.5 parts of 2-chlorothioxanthone.
• the coating which was 15 ⁇ m thick, was irradiated at a distance of 3 cm for 15 seconds in the first stage and, at a distance of 25 cm., for 45 seconds in the next stage, with a metal halide lamp of 5000 watts. On development with benzyl alcohol a good image was obtained.
• Example 2 The procedure of Example 1 was repeated, using a composition which comprised 30 parts of N-(2-(2-(methacryloyloxy)ethoxy)ethyl)-2,3-dimethylmaleimide, 50 parts of 3-(methacryloyloxy)-2-hydroxypropyl, X,Y-dibromo-p-cresyl ether, 20 parts of glycidyl methacrylate, 4 parts of benzil dimethyl ketal, and 2 parts of 2-chlorothioxanthone, applied as a coating 4 ⁇ m thick. The coating became nontacky on irradiation for 10 seconds in the first stage.
• a mixture comprising 40 parts of 2-(acryloyloxy)ethyl 3-(methacryloyloxy)-2-hydroxypropyl X-(2,3-dimethylmaleimido)phthalates, 2.4 parts of benzil dimethyl ketal, 1.2 parts of 2-chlorothioxanthone, and 10 parts of glycidyl methacrylate, in the form of a coating on a copper plate, was irradiated for 40 seconds with a medium pressure mercury lamp (80 w per cm) at a distance of 20 cm, a non-tacky coating being obtained. On irradiation at a distance of 25 cm for 15 minutes with a medium pressure mercury lamp (30 w per cm) followed by development with acetone-toluene (1:9 by volume) an image was obtained.
• a medium pressure mercury lamp 80 w per cm
• the formulation contains a dye so that the image could be clearly seen.
• Example 6 The procedure of Example 6 was repeated, the N-(2-(acryloyloxy)ethyl)-2,3-dimethylmaleimide being replaced by an equal weight of N-(2-(methacryloyloxy)ethyl)-2,3-dimethylmaleimide with similar results.
• the formulation contains methacrylic acid, so that the image may be developed by means of an aqueous basic solution.
• a composition comprising 23 parts of N-(2-(acryloyloxy)ethyl)-2,3-dimethylmaleimide, 23 parts of methacrylic acid, 46 parts of 3-(methacryloyloxy)-2-hydroxypropyl X,Y-dibromo-p-cresyl ether, 6 parts of benzil dimethyl ketal, and 2 parts of 2-chlorothioxanthone was irradiated as described in Example 2, followed by development with 0.1 M aqueous sodium hydroxide. A good relief image was obtained.
• the formulation contains 2-(diethylamino)ethyl acrylate so that the image may be developed by means of an aqueous acidic solution.
• a composition comprising 30 parts of N-(2-(2-(methacryloyloxy)ethoxy)ethyl)-2,3-dimethylmaleimide, 20 parts of 3-(methacryloyloxy)-2-hydroxypropyl X,Y-dibromo-p-cresyl ether, 50 parts of 2-(diethylamino)ethyl acrylate, 3 parts of benzil dimethyl ketal, and 1.5 parts of 2-chlorothioxanthone was applied as a coating 4 ⁇ m thick onto copper plate.
• the coating was irradiated for 10 seconds with a medium pressure mercury lamp (80 w per cm) at a distance of 20 cm, and it became nontacky. After the coating had been irradiated through a negative with a medium pressure mercury lamp (30 w per cm) at a distance of 25 cm for 20 minutes the image was developed by means of 1 M hydrochloric acid.
• composition contains a latent curing agent for epoxide resins so that the developed image could be heat-cured.
• a mixture having a viscosity of approximately 0.3 Pa s and comprising 25 parts of N-(2-(methacryloyloxy)ethyl-2,3-dimethylmaleimide, 52 parts of 3-(methacryloyloxy)-2-hydroxypropyl X,Y-dibromo-p-cresyl ether, 12 parts of glycidyl acrylate, 6 parts of benzil dimethyl ketal, 2 parts of 2-chlorothioxanthone, and 3 parts of 2,6-xylidene biguanide was applied to a copper plate as described in Example 1 and then irradiated under the two sets of conditions described in that Example. After development with cyclohexanone the plate was heated at 170° C. for 1 hour to heat-cure the product through its epoxide groups.
• a mixture comprising 50 parts of n-[p-(acryloylamino)phenyl]-2,3-dimethylmaleimide, 100 parts of glycidyl acrylate, 6 parts of benzil dimethyl ketal, and 3 parts of 2-chlorothioxanthone was applied as in example 1 except that the layer was irradiated for 60 seconds in the first stage and for 30 minutes in the second stage. On development with 1,1,1-trichloroethane with brushing an image was obtained.
• composition containing 60 parts of N-(3-hydroxypropyl)-2,3-dimethylmaleimide. 64 parts of 3-(methacryloyloxy)-2-hydroxypropyl, X,Y-dibromo-p-cresyl ether, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of benzil dimethyl ketal, and 5 parts of 2-chlorthioxanthone.
• This composition was applied as a coating 10 ⁇ m thick to a copper-clad epoxide resin-glass fibre laminate and irradiated with a medium pressure mercury lamp (80 w per cm) for 25 seconds, a tack-free film being obtained.
• a medium pressure mercury lamp 80 w per cm

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• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
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• Photosensitive Polymer And Photoresist Processing (AREA)

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• 1982
  • 1982-03-25 US US06/361,702 patent/US4416975A/en not_active Expired - Fee Related
  • 1982-03-29 EP EP82810139A patent/EP0062610B1/de not_active Expired
  • 1982-03-29 DE DE8282810139T patent/DE3263228D1/de not_active Expired
  • 1982-03-31 CA CA000400312A patent/CA1178479A/en not_active Expired
  • 1982-04-01 ES ES511035A patent/ES511035A0/es active Granted
  • 1982-04-02 JP JP57055273A patent/JPS57177140A/ja active Pending

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